JP2002363146A - Basic compound, resist material and pattern-forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resist material having higher contrast, i.e., a wider focus margin, and capable of solving the problem of size ratio of a close-packed pattern and an isolated pattern, and further to provide a pattern-forming method by using the resist material. SOLUTION: This basic compound is represented by general formula (1), (2) or (3). The resist material is characterized in that the resist material contains one or more kinds of the basic compounds selected from the group consisting of general formulas (5) to (9). The pattern-forming method comprises a step for coating the resist material on a substrate, a step for exposing the coated film after heat treatment through a photomask to high-energy rays having <=300 nm wavelength or an electron beam, and a step for carrying out the development by using a developing solution optionally after heat treating.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] 1. Field of the Invention [0002] The present invention relates to a novel chemically amplified positive resist material suitable for fine processing technology and a pattern forming method using the same.

[0002]

2. Description of the Related Art Along with the high integration and high speed of LSIs, there is a demand for finer pattern rules, and far-ultraviolet lithography is expected as a next-generation fine processing technology. In the deep ultraviolet lithography, processing of 0.2 μm or less is possible, and when a resist material having low light absorption is used, a pattern having side walls nearly perpendicular to the substrate can be formed. In recent years, a technique using a high-brightness KrF excimer laser as a light source of far ultraviolet has attracted attention. In order to use this technique as a mass production technique, a resist material having low light absorption and high sensitivity has been demanded. ing.

[0003] From such a viewpoint, an acid-catalyzed chemically amplified positive resist material recently developed (Japanese Patent Publication No. 2-2)
No. 7660, described in JP-A-63-27829, etc.)
Is a resist material that has high sensitivity, resolution, and dry etching resistance and has excellent characteristics, and is particularly promising for deep ultraviolet lithography.

As a drawback of the chemically amplified resist, if the exposure time from exposure to PEB (Post Exposure Bake) becomes longer, the line pattern becomes T-top shape when the pattern is formed, that is, the upper part of the pattern becomes thicker. [PED (Post Expos
ure delay), or a so-called footing phenomenon in which a pattern near a basic substrate, particularly a silicon nitride or titanium nitride substrate, becomes thicker. T-
The top phenomenon is considered to be due to the decrease in the solubility of the resist film surface, and the tailing on the substrate surface is considered to be due to the decrease in the solubility near the substrate. Further, a dark reaction of elimination of the acid labile group progresses from the exposure to the PEB, resulting in a problem that the remaining dimension of the line is reduced. These are major drawbacks when a chemically amplified resist is put to practical use. Due to this drawback, the conventional chemically amplified positive resist material has a problem that it is difficult to control the dimensions in the lithography process, and the dimensions are impaired even when processing the substrate using dry etching.
Hinsberg, et. al. , J. et al. Photopo
lym. Sci. Technol. , 6 (4), 535
-546 (1993). , T .; Kumada, et. a
l. , J. et al. Photopolym. Sci. Techn
ol. , 6 (4), 571-574 (1993). ].

In a chemically amplified positive resist material, P
It is considered that the cause of the problem of ED or footing of the substrate surface largely depends on a basic compound in the air or on the substrate surface. The acid on the resist film surface generated by the exposure reacts and deactivates with the basic compound in the air, and the longer the standing time until PEB, the more the deactivated acid increases. Is less likely to occur. Therefore, a hardly-solubilized layer is formed on the surface, and the pattern has a T-top shape.

[0006] Here, it is well known that the addition of a basic compound can suppress the influence of the basic compound in the air, and thus has an effect also on PED (US Pat. No. 5,609,989, WO 98/37458). issue,
JP-A-63-149640, JP-A-5-113666
Nos. 5,232,706 and 5-249,662).

As the basic compound, a nitrogen-containing compound is well known, and examples thereof include an amine compound or an amide compound having a boiling point of 150 ° C. or higher. Specifically, pyridine, polyvinylpyridine, aniline, N-methylaniline, N, N-dimethylaniline, o-toluidine, m-
Toluidine, p-toluidine, 2,4-lutidine, quinoline, isoquinoline, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, 2-pyrrolidone, N- Methylpyrrolidone, imidazole, α-picoline, β-picoline, γ-picoline, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, 1,2-phenylenediamine, 1,3-
Phenylenediamine, 1,4-phenylenediamine, 2
And triazine compounds such as -quinolinecarboxylic acid, 2-amino-4-nitrophenol, and 2- (p-chlorophenyl) -4,6-trichloromethyl-s-triazine. Among these, pyrrolidone, N-methylpyrrolidone, o-aminobenzoic acid, m-aminobenzoic acid, p-aminobenzoic acid, and 1,2-phenylenediamine are particularly exemplified.

However, these nitrogen-containing compounds are weak bases and can alleviate the T-Top problem, but control the reaction when a highly reactive acid labile group, for example, an acetal group such as 1-ethoxyethyl, is used. That is, the acid diffusion cannot be controlled. Addition of a weak base, in particular, caused the dark reaction in the PED to proceed in the unexposed part, causing a reduction in the line size (slimming) of the acetal-based acid leaving group and a decrease in the film thickness on the line surface. To solve the above problem, it was effective to add a strong base. However, the higher the basicity, the better it is.
Sufficient effects could not be obtained even with the addition of quaternary amines such as N or proton sponge or tetramethylammonium halide oxide.

The effects of adding a basic compound to a resist composition include not only improvement in environmental stability but also improvement in resolution. Although the sensitivity is reduced by the addition of a base, the contrast of acid generation is improved. In the exposed region where the number of moles of the generated acid is smaller than the number of moles of the base added, the acid is lost by neutralizing with the base and the catalyst cannot be caused to react. An acid is generated, causing a catalytic reaction. The rapid acid generation phenomenon near the neutralization point due to the addition of base was described by Hatakeyama et al. In SPIE symp. Proc., 33
33, 62, (1998) called it a proton jump.
Hatakeyama et al. Examined the mechanism of proton jump in detail, and found that J. Potopoly. Sci. Technol., Vol13,
(4), p519 (2000) proposed a competitive reaction theory in which a neutralization reaction between an acid and a base generated by exposure and an acid-catalyzed reaction occur simultaneously. Here, the neutralization reaction between the photogenerated acid and the added base was kinetically solved, and it was shown that a base having a larger reaction rate constant of the neutralization reaction had higher contrast.

The present inventors have conducted experiments with the addition of various bases and found that the reaction rate constant with an acid and pKa are not particularly closely related. For example, DBU (1,8-Diazabicyclo [5.4.0] -7-undecene) or DBN (1,5-Diazabicyclo [4.3.0] -5-nonene), which is called a super strong base, or a proton sponge or Triethanolamine, which is less basic, obtained a higher reaction rate constant than quaternary amines such as tetramethylammonium hydroxide or sodium hydroxide and potassium hydroxide. Furthermore, tris ｛2-
(Methoxymethoxy) ethyl diamine, tris [2-
{(2-Methoxyethoxy) methoxy} ethyl] amine is more preferred than tris {2- (acetoxy) ethyl} amine and N, N-bis (2-acetoxyethyl) -3-aminopropanol over the aforementioned substances. Ononitrile had a higher reaction rate and higher contrast. Incidentally, the pKa of these bases is estimated to be around 7, and is much weaker than DBU or DBN of about 13, or quaternary ammonium hydroxide or proton sponge.

[0011]

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As a result, the base to be added to the resist does not need to be a particularly strong base, and may be a hydroxyl group, an ether group, especially an ester group, a carbonyl group, a carbonate group, a cyano group, a lactone ring or other water. Although amines having a compatible group have been found to be effective, resist materials having even higher contrast are required.

On the other hand, in recent years, the dimensional ratio between the dense pattern and the isolated pattern has become a problem. Even if the dimensions on the mask are the same, there is a dimensional difference between the dense pattern after development and the isolated pattern. The above problem is particularly serious in dimensions exceeding the wavelength. This is because the optical intensity differs due to the difference in light interference between the dense pattern and the isolated pattern in image formation. For example, wavelength 248 nm, NA 0.6,
FIG. 1 shows the dimensions when the pitch of the 0.18 micron line was changed under the optical conditions of σ0.75. If the line size is normalized to be 0.18 microns with a 0.36 micron pitch (0.18 micron line, 0.18 micron space), the optical image size (Aerial Image)
g) becomes thinner and thicker as the pitch increases.

FIG. 1 also shows the results of measuring the resist dimensions after development. The resist dimensions were determined by the simulation software PROLITH2Ver. Sold by KLA-Tencor (former Finli). 6.0 was used. The resist dimensions become thinner as the pitch increases and further narrower as the acid diffusion length increases (25-70 nm). The problem of coarse / dense dependency, in which the size of an isolated pattern is smaller than that of a dense pattern, is becoming more serious. It can be understood from the simulation results that the method of reducing the acid diffusion is effective as a method of reducing the density dependence. However, if the acid diffusion is made too small, the sidewalls of the developed resist pattern may have irregularities or rough surfaces due to standing waves, or may have problems of increased line edge roughness. There is a method of using an acid generator having an appropriate diffusion distance in order to reduce the line roughness, but this method cannot further improve the density dependence.

[0015]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and has a higher contrast, that is, a wider focus margin, and a resist material which has solved the problem of the dimensional ratio between a dense pattern and an isolated pattern. And a pattern forming method using the same.

[0016]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, a basic compound having an aryl group and a hydratable group in one molecule achieves the above object. It was found to be extremely effective above. That is,
Considering the diffusion of the base, the opposite result to the acid diffusion is expected. It is considered that the larger the base diffusion is, the thicker the isolated line becomes, and the coarse / dense dependency is improved. Furthermore, the diffusion of the base can be expected to reduce unevenness and line edge roughness due to low standing waves due to the smoothing effect. The present inventors consider that the diffusion of a base having an aryl group is relatively large, and an aryl group that expands base diffusion and a hydroxy group having a high reaction rate with an acid, an ether group, particularly an ester group,
The inventors have found that a base having a hydratable group such as a carbonyl group, a carbonate group, a cyano group, and a lactone ring in one molecule is extremely effective, and have reached the present invention.

First, the present invention provides basic compounds represented by the following general formulas (1), (2) and (3).

Embedded image (In the above formula, R ⁰ is a linear or branched alkyl group having 1 to 6 carbon atoms, and may include a hydroxy group, an ether group, a carbonyl group, an ester group, a lactone ring, or a carbonate group. Is independently 1 or 2, and b is independently 1 or 2. In each compound, a + b = 3 is satisfied. X is an oxygen atom or a sulfur atom.) There is provided a resist material comprising one or more basic compounds selected from the group consisting of the following general formulas (5) to (9).

Embedded image (Wherein R ¹ is independently an aryl or aralkyl group having 6 to 20 carbon atoms, such as a hydroxy group, an ether group,
It may contain a carbonyl group, an ester group, a lactone ring, or a carbonate group. R ² , R ⁴ and R ⁷ are each independently a linear or branched alkylene group having 1 to 4 carbon atoms. R ³ and R ⁶ are each independently a hydrogen atom or a group having 1 to 20 carbon atoms.
A linear, branched or cyclic alkyl group or alkoxy group, which may contain a hydroxy group, an ether group, a carbonyl group, an ester group, a lactone ring, or a carbonate group, and R ⁵ is independently Single bond or carbon number 1
To 20 linear, branched or cyclic alkyl groups. R ⁸ is independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, including a hydroxy group, an ether group, a carbonyl group, an ester group, a lactone ring, a carbonate group, or a cyano group. You can go out. R ⁷ and R ⁸ may combine with each other to form a ring. R ⁹ is a linear or branched alkylene group having 1 to 20 carbon atoms,
It may contain a hydroxy group, an ether group, a carbonyl group, an ester group, a thioether group, and a carbonate group. a is independently 1 or 2, and b is independently 1 or 2, but a + b = 3 in each compound. Also, (A) a basic compound selected from the group consisting of the general formulas (5) to (9), (B) an organic solvent, and (C1) an alkali having an acidic functional group protected by an acid labile group. A positive resist material containing a base resin, which is an insoluble or hardly soluble resin and becomes alkali-soluble when the acid labile group is eliminated, and (D) an acid generator; A positive resist material containing an inhibitor is provided. Further, (A) a basic compound selected from the group consisting of general formulas (5) to (9), (B) an organic solvent,
(C2) a base resin which is an alkali-soluble resin, and which becomes hardly soluble in alkali by crosslinking with a crosslinking agent;
Provided is a negative resist material comprising an acid generator and (F) a crosslinking agent which is crosslinked by an acid. In addition, alkali insoluble or alkali hardly soluble, at 10-30 ° C.,
Solubility in 2.38 wt% TMAH (tetramethylammonium hydroxide) aqueous solution is 0 to 20 ° / sec.
Less than and alkali-soluble is 20 to 30,000
Å / sec. Further, (1) a step of applying these chemically amplified resist materials on a substrate, and (2) a step of exposing with a high-energy ray or an electron beam having a wavelength of 300 nm or less through a photomask after a heat treatment,
(3) a step of performing a heat treatment as needed and then developing with a developer.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The aryl group or aralkyl group having 6 to 20 carbon atoms represented by R ¹ in the general formulas (5) to (8) can be represented by the following general formulas (4) -1 to (4) -2.

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In the general formulas (4) -1 and (4) -2, R ¹⁰ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group,
They are an aralkyl group, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, a cyano group, an ester group, and an acetoxy group, and x and y are integers satisfying 0 ≦ x ≦ 5 and 0 ≦ y ≦ 7. R ¹¹ is a single bond or a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms.

A base having a phenyl group is mainly used for a KrF excimer laser, and a base having a naphthyl group is preferably used because of its high transparency in ArF excimer laser light.

The substituents in parentheses b in the general formulas (5) to (8) are specifically represented by the following formulas (5) -1 to (5) -4;
(6) -1 to (6) -11, (7) -1 to (7) -2
4, (8) -1.

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[0022]

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[0023]

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[0024]

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R ⁹ in the general formula (9) has 1 to 2 carbon atoms.
0 linear or branched alkylene group, and at least one or more hydroxy group, ether group, carbonyl group,
It contains an ester group, a thioether group and a carbonate group, and specific examples of the cyclic structure comprising R ⁹ and a nitrogen atom include the following (9) -1 to (9) -9.

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A typical method for synthesizing the base of the present invention is illustrated below. The basic compounds of the present invention represented by the general formulas (1), (2) and (3) can be produced by, for example, the following methods, but are not limited thereto. The details will be described below.

The basic compounds of the present invention represented by the general formulas (1) and (2) can be efficiently synthesized by an addition reaction of benzylamine or dibenzylamine to an acrylate compound and acrylonitrile, respectively.

Embedded image (In the formula, R ⁰ , a, and b are the same as described above.)

The amount of the acrylate compound (S2) and the amount of the acrylonitrile (S3) to be used is 1.0 when a = 1, that is, when the amine compound (S1) is benzylamine, per mole of the amine compound (S1). -10
Mole, especially 1.6 to 2.4 mole,
When a = 2, that is, when the amine compound (S1) is dibenzylamine, 0.5 to 5.0 mol, particularly 0.8 to 5.0 mol
Desirably, it is 1.2 mol. The reaction is performed without solvent or in a solvent. As the solvent, methanol, ethanol, isopropyl alcohol, t-butyl alcohol,
Alcohols such as ethylene glycol, hydrocarbons such as hexane, heptane, benzene, toluene, xylene, ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, diglyme, methylene chloride, chloroform, 1.2 Aprotic polar solvents such as chlorinated solvents such as -dichloroethylene, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide and N-methylpyrrolidone; carboxylic acids such as formic acid and acetic acid; ethyl acetate;
Either butyl acetate or other esters, acetone, 2-butanone or other ketones, acetonitrile or other nitriles, pyridine, triethylamine or other amines, or water can be used alone or as a mixture depending on the reaction conditions. it can. The reaction temperature is selected in the range from 0 ° C. to the reflux temperature of the solvent according to the reaction rate. In the reaction, inorganic acids such as hydrochloric acid, sulfuric acid, and nitric acid or salts thereof, p-toluenesulfonic acid, formic acid, acetic acid, oxalic acid, and organic acids such as trifluoroacetic acid or the like as catalysts to improve the reaction rate. May be added. Further, in order to prevent polymerization of the acrylate compound and acrylonitrile, hydroquinone, p-methoxyphenol,
A polymerization inhibitor such as benzoquinone or phenylenediamine may be added. The reaction time is preferably from 2 to 200 hours, although it is desirable from the viewpoint of the yield to follow the reaction by gas chromatography (GC) or thin layer chromatography (TLC) to complete the reaction. The reaction mixture can be used directly or by usual aqueous work-up (aqueous wo
After rk-up), the mixture is concentrated under reduced pressure to obtain the desired basic compound (1) or (2). If necessary, the obtained basic compound (1) or (2) can be purified by a conventional method such as distillation, chromatography, and recrystallization.

The basic compound of the present invention represented by the general formula (3) can be efficiently synthesized by benzylation of morpholine or thiomorpholine with a benzyl halide.

Embedded image (In the above formula, X is the same as described above. Y represents a halogen atom.)

The amount of the benzyl halide (S4) used is
The amount is preferably 0.2 to 15 mol, particularly 0.4 to 1.2 mol, per 1 mol of the amine compound (S5). The reaction is performed without solvent or in a solvent. Examples of the solvent include alcohols such as methanol, ethanol, isopropyl alcohol, t-butyl alcohol, and ethylene glycol; hydrocarbons such as hexane, heptane, benzene, toluene, and xylene; diethyl ether, dibutyl ether, tetrahydrofuran, and 1,4- Ethers such as dioxane and diglyme, methylene chloride, chloroform,
Chlorinated solvents such as 1,2-dichloroethylene, N, N
Aprotic polar solvents such as -dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, carboxylic acids such as formic acid and acetic acid, esters such as ethyl acetate and butyl acetate, acetone and 2-butanone; And a mixture of ketones, nitriles such as acetonitrile, and water depending on the reaction conditions. Other basic compounds may be added to promote the reaction. Examples of other basic compounds include tertiary amines such as pyridine, triethylamine, and 4-dimethylaminopyridine, sodium hydroxide, and hydroxide. Examples include inorganic hydroxides such as potassium, metal carbonates such as sodium carbonate and potassium carbonate, metal hydrides such as sodium hydride, and alkyl metals such as butyllithium. The amount of other basic compounds used is
0.8 to 10 based on 1 mol of benzyl halide (S4)
Desirably, the amount is 1.0 to 5.0 moles. The reaction temperature is selected in the range from 0 ° C. to the reflux temperature of the solvent according to the reaction rate. The reaction time is desirably traced by gas chromatography (GC) or thin-layer chromatography (TLC) to complete the reaction in view of the yield, but is usually about 2 to 200 hours. The target basic compound (3) is obtained by removing the solid matter from the reaction mixture by filtration, or by concentrating the mixture under reduced pressure after usual aqueous work-up. The obtained basic compound (3) can be purified by distillation if necessary.

(B) used in the resist material of the present invention
The organic solvent of the component may be any organic solvent that can dissolve the acid generator, the base resin, the dissolution inhibitor and the like.
Examples of such an organic solvent include ketones such as cyclohexanone and methyl-2-n-amyl ketone;
Alcohols such as methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol Ethers such as monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, and 3-ethoxypropionic acid Ethyl, tert-acetic acid
-Butyl, tert-butyl propionate, esters such as propylene glycol-mono-tert-butyl ether acetate, and lactones such as γ-butyrolactone. One of these may be used alone or as a mixture of two or more. However, the present invention is not limited to these. In the present invention, among these organic solvents, diethylene glycol dimethyl ether and 1-ethoxy-2 which have the best solubility of the acid generator in the resist component are used.
-In addition to propanol and ethyl lactate, propylene glycol monomethyl ether acetate which is a safe solvent and a mixed solvent thereof are preferably used.

The base polymers mentioned as the components (C1) and (C2) are polyhydroxystyrene (PHS) for resist for KrF excimer laser, and PHS and styrene, indene, (meth) acrylate, maleimide N For copolymers with carboxylic acid esters, for EB, EUV, and X-ray, in addition to the above polymers, polyhydroxyvinylnaphthalene, polyhydroxyvinylanthracene, acenaphthene and the like can be mentioned.
RF excimer laser resists include (meth) acrylate esters, alternating copolymers of norbornene and maleic anhydride, alternating copolymers of tetracyclododecene and maleic anhydride, polynorbornenes, and ring-opening polymerization. metathesis polymerization system by, the KrF for the F ₂ excimer laser, a fluorine-substituted body ArF polymers and is like a copolymer of tetrafluoroethylene, but is not limited to these polymerization type polymer. In addition, (meth) acrylic acid is an abbreviation for methacrylic acid or acrylic acid. In the case of a positive resist, the dissolution rate of an unexposed portion is generally reduced by replacing a hydrogen atom of a phenol or carboxyl group or a hydroxyl group of a fluorinated alkyl alcohol with an acid labile group.

The acid labile group of the base polymer and the acid labile group of the basic compound in the present invention are variously selected, but the same ones can be mentioned. In particular, the following formula (10),
A group represented by (11), a tertiary alkyl group having 4 to 40 carbon atoms, a trialkylsilyl group having 1 to 6 carbon atoms, an oxoalkyl group having 4 to 20 carbon atoms, and the like represented by the following formula (12). Is preferred.

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In the formulas (10) and (11), R ¹² and R ¹⁵
Is a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and may contain a hetero atom such as oxygen, sulfur, nitrogen, or fluorine. R ¹³ and R ^{14 each} represent a hydrogen atom, having 1 to 20 carbon atoms.
Linear, branched, or cyclic alkyl group, which may contain a heteroatom such as oxygen, sulfur, nitrogen, or fluorine; c
Is an integer of 0 to 10. R ¹³ and R ^14, R ¹³ and R ^15, R
¹⁴ and R ¹⁵ may be bonded to each other to form a ring. In the formula (12), R ¹⁶ , R ¹⁷ and R ^{18 each} have 1 to 20 carbon atoms.
Is a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group, and may contain a heteroatom such as oxygen, sulfur, nitrogen, or fluorine; R ¹⁶ and R ¹⁷ , R ¹⁶ and R ¹⁸ , R ¹⁷
And R ¹⁸ may combine with each other to form a ring.

Specific examples of the acid labile group represented by the formula (10) include a tert-butoxycarbonyl group and te
rt-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2
-Tetrahydropyranyloxycarbonylmethyl group, 2
-A tetrahydrofuranyloxycarbonylmethyl group or the like,
Further, substituents represented by the following general formulas (10) -1 to (10) -9 can be mentioned.

[0036]

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In the formulas (10) -1 to (10) -9, R ¹⁹ is the same or non-identical linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and 6 to 20 carbon atoms. Represents an aryl group. R ²⁰ is absent or represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²¹ represents an aryl group having 6 to 20 carbon atoms. The acid labile groups represented by the formula (11) are exemplified by (11) -1 to (11) -23.

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Also, one of the hydrogen atoms of the hydroxyl group of the base resin
Mole% or more may be cross-linked intramolecularly or intramolecularly by an acid labile group represented by the general formula (11a) or (11b).

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In the formula, R ²² and R ²³ represent a hydrogen atom or a carbon atom
-8 represents a linear, branched or cyclic alkyl group. Alternatively, R ²² and R ²³ may combine to form a ring, and when forming a ring, R ²² and R ²³ have 1 to 8 carbon atoms.
Represents a linear or branched alkylene group. R ²⁴ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and e is 0 or an integer of 1 to 10. A represents a d + 1-valent aliphatic or alicyclic saturated hydrocarbon group having 1 to 50 carbon atoms, an aromatic hydrocarbon group or a heterocyclic group, and these groups may have a hetero atom interposed; A part of the hydrogen atom bonded to the carbon atom may be substituted by a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B is -CO-O-, -NHCO-O- or NHCO
Shows NH-. d is an integer of 1 to 7.

The crosslinked acetal represented by the general formulas (11a) and (11b) is specifically exemplified by the following (11) -24 to
(11) -31.

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The tertiary alkyl group represented by the formula (12) includes a tert-butyl group, a triethylcarbyl group,
-Ethylnorbonyl group, 1-methylcyclohexyl group,
1-ethylcyclopentyl group, 2- (2-methyl) adamantyl group, 2- (2-ethyl) adamantyl group, te
rt-amyl group, or the following (12) -1 to (12)
-18.

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In the formula, R ²⁵ has the same or non-identical carbon number of 1 to
8 linear, branched or cyclic alkyl groups, 6 carbon atoms
-20 to 20 aryl groups. R ²⁶ and R ²⁸ do not exist or represent a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ²⁷ represents an aryl group having 6 to 20 carbon atoms.

[0043] Further (12) -19, as shown in (12) -20, divalent or more alkylene groups, including R ²⁹ is an arylene group, even within the molecule or between molecules of the polymer are crosslinked good. In the formula (12) -19, R ²⁵ is the same as described above, and R ²⁹ represents a linear, branched, or cyclic alkylene group or arylene group having 1 to 20 carbon atoms, such as an oxygen atom, a sulfur atom, or a nitrogen atom. It may contain a hetero atom. f
Is an integer of 1 to 3.

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Further, R ²⁵ , R ²⁶ , R ²⁷ and R ²⁸ are oxygen,
It may have a hetero atom such as nitrogen or sulfur, and specific examples thereof are shown in (13) -1 to (13) -7 below.

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As the acid labile group, a trialkylsilyl group having 1 to 6 carbon atoms can be used. As the trialkylsilyl group having 1 to 6 carbon atoms, a trimethylsilyl group,
Examples include a triethylsilyl group and a dimethyl-tert-butylsilyl group. 4-20 carbon atoms as acid labile group
An oxoalkyl group of the formula
Examples of the oxoalkyl group of No. to No. 20 include a 3-oxocyclohexyl group or a group represented by the following formula.

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The weight average molecular weight of the base polymer is from 5,000 to 10 when measured by gel permeation chromatography (GPC) in terms of polystyrene.
It is preferably set to 000, and if it is less than 5,000, the film formability and the resolution may be poor.
If it exceeds, the resolution may be poor.

Examples of the acid generator (D) include an onium salt of the following general formula (14), a diazomethane derivative of the formula (15), a glyoxime derivative of the formula (16), a β-ketosulfone derivative, a disulfone derivative, and nitrobenzyl. Sulfonate derivatives, sulfonic acid ester derivatives, imido-yl sulfonate derivatives, and the like.

[0048]

Embedded image (However, R ³⁰ represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, and M ⁺ represents iodonium, sulfonium. And K ⁻ represents a non-nucleophilic counter ion, and g is 2 or 3.)

Examples of the alkyl group for R ³⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a cyclohexyl group,
An oxocyclohexyl group, a norbornyl group, an adamantyl group and the like can be mentioned. As the aryl group, a phenyl group,
p-methoxyphenyl group, m-methoxyphenyl group, o
-Methoxyphenyl group, ethoxyphenyl group, p-te
an alkoxyphenyl group such as an rt-butoxyphenyl group, an m-tert-butoxyphenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group,
Ethylphenyl group, 4-tert-butylphenyl group,
Examples thereof include an alkylphenyl group such as a 4-butylphenyl group and a dimethylphenyl group. Examples of the aralkyl group include a benzyl group and a phenethyl group. K ^- a non-nucleophilic counter chloride ions as the ion, halide ions such as bromide ion, triflate, 1,1,1-trifluoroethane sulfonate, fluoroalkyl sulfonate such as nonafluorobutanesulfonate, tosylate, benzenesulfonate , 4-fluorobenzenesulfonate, arylsulfonates such as 1,2,3,4,5-pentafluorobenzenesulfonate, and alkylsulfonates such as mesylate and butanesulfonate.

[0050]

Embedded image (However, R ³¹ and R ³² are a linear, branched or cyclic alkyl group or halogenated alkyl group having 1 to 12 carbon atoms, an aryl group or halogenated aryl group having 6 to 12 carbon atoms, or a C ⁷ to C 12 12 represents an aralkyl group)

Examples of the alkyl group of R ³¹ and R ³² include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group and an adamantyl group. Examples of the halogenated alkyl group include a trifluoromethyl group, a 1,1,1-trifluoroethyl group, a 1,1,1-trichloroethyl group, a nonafluorobutyl group, and the like. Examples of the aryl group include phenyl, p-methoxyphenyl, m-methoxyphenyl, o-methoxyphenyl, ethoxyphenyl, p-tert-butoxyphenyl, and m-tert.
An alkoxyphenyl group such as -butoxyphenyl group, 2-
Examples thereof include an alkylphenyl group such as a methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, an ethylphenyl group, a 4-tert-butylphenyl group, a 4-butylphenyl group, and a dimethylphenyl group. Examples of the halogenated aryl group include a fluorobenzene group, a chlorobenzene group, a 1,2,3,4,5-pentafluorobenzene group, and the like. Examples of the aralkyl group include a benzyl group and a phenethyl group.

[0052]

Embedded image (However, R ³³ , R ³⁴ , and R ³⁵ are linear having 1 to 12 carbon atoms;
It represents a branched or cyclic alkyl group or a halogenated alkyl group, an aryl group having 6 to 12 carbon atoms, an aryl halide group or an aralkyl group having 7 to 12 carbon atoms. Also,
R ³⁴ and R ³⁵ may combine with each other to form a cyclic structure, and when forming a cyclic structure, R ³⁴ and R ³⁵ each represent a linear or branched alkylene group having 1 to 6 carbon atoms. . )

As the alkyl group, halogenated alkyl group, aryl group, halogenated aryl group and aralkyl group of R ³³ , R ³⁴ and R ³⁵ , the same groups as described for R ³¹ and R ³² can be mentioned. The alkylene group for R ³⁴ and R ³⁵ includes a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and the like.

Examples of the onium salts include diphenyliodonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) phenyliodonium trifluoromethanesulfonate, diphenyliodonium p-toluenesulfonate, and p-toluenesulfonic acid (p-toluenesulfonic acid).
tert-butoxyphenyl) phenyliodonium,
Triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, bis (p-tert-butoxyphenyl) phenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxy) trifluoromethanesulfonate Phenyl) sulfonium, triphenylsulfonium p-toluenesulfonate, diphenylsulfonium p-toluenesulfonate (p-tert-butoxyphenyl), bis (p-tert-butoxyphenyl) phenylsulfonium p-toluenesulfonate, p-toluenesulfonate Tris (p-tert-butoxyphenyl) sulfonium acid, triphenylsulfonium nonafluorobutanesulfonate, butanesulfonic acid Li phenyl trifluoromethanesulfonate, trimethylsulfonium, p
-Trimethylsulfonium toluenesulfonate, cyclohexylmethyl trifluoromethanesulfonate (2-oxocyclohexyl) sulfonium, cyclohexylmethyl p-toluenesulfonate (2-oxocyclohexyl) sulfonium, dimethylphenylsulfonium trifluoromethanesulfonate, dimethyl p-toluenesulfonate Examples include phenylsulfonium, dicyclohexylphenylsulfonium trifluoromethanesulfonate, and dicyclohexylphenylsulfonium p-toluenesulfonate.

As the diazomethane derivative, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl)
Diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (se
c-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-amylsulfonyl)
Diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis (tert-amylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-
(Butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-amylsulfonyl) diazomethane, 1-tert-amylsulfonyl-1- (t
tert-butylsulfonyl) diazomethane and the like.

Glyoxime derivatives include bis-o-
(P-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-o
-(P-toluenesulfonyl) -2,3-pentanedione glyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (n-butanesulfonyl) ) -Α-dimethylglyoxime, bis-o- (n-butanesulfonyl)
-Α-diphenylglyoxime, bis-o- (n-butanesulfonyl) -α-dicyclohexylglyoxime,
Bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxime, bis-o- (methane Sulfonyl) -α-dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-o- (1,
1,1-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-o- (tert-butanesulfonyl) -α-dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylglyoxime, Bis-o- (cyclohexanesulfonyl) -α-
Dimethylglyoxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) -Α-dimethylglyoxime, bis-o- (xylenesulfonyl) -α-dimethylglyoxime, bis-
o- (Camphorsulfonyl) -α-dimethylglyoxime and the like.

The β-ketosulfone derivatives include 2-cyclohexylcarbonyl-2- (p-toluenesulfonyl) propane and 2-isopropylcarbonyl-2- (p
-Toluenesulfonyl) propane and the like.

Examples of the nitrobenzylsulfonate derivative include disulfone derivatives such as diphenyldisulfone and dicyclohexyldisulfone, p-toluenesulfonic acid 2,
6-dinitrobenzyl, p-toluenesulfonic acid 2,4
-Dinitrobenzyl and the like.

Examples of the sulfonic acid ester derivatives include 1,
2,3-tris (methanesulfonyloxy) benzene,
Examples thereof include 1,2,3-tris (trifluoromethanesulfonyloxy) benzene and 1,2,3-tris (p-toluenesulfonyloxy) benzene.

The imido-yl-sulfonate derivatives include phthalimido-yl-triflate, phthalimido-yl-tosylate, 5-norbornene-2,3-dicarboximido-yl-triflate, 5-norbornene-2,3- Dicarboximido-yl-tosylate,
5-norbornene-2,3-dicarboximido-yl-n-butylsulfonate and the like.

Preferably, triphenylsulfonium trifluoromethanesulfonate, trifluoromethanesulfonic acid (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, p
-Triphenylsulfonium toluenesulfonate, p-
Onium salts such as toluenesulfonate (p-tert-butoxyphenyl) diphenylsulfonium, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, bis (benzenesulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, Bis (cyclohexylsulfonyl) diazomethane,
Bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, etc. Diazomethane derivative of bis-o-
Glyoxime derivatives such as (p-toluenesulfonyl) -α-dimethylglyoxime and bis-o- (n-butanesulfonyl) -α-dimethylglyoxime, and naphthoquinonediazidesulfonic acid ester derivatives are used.

The above-mentioned acid generators may be used alone or in combination.
More than one species can be used in combination. The onium salt is excellent in the effect of improving the rectangularity, and the diazomethane derivative and the glyoxime derivative are excellent in the standing wave reducing effect. However, the fine adjustment of the profile can be performed by combining the two. The amount of the acid generator is based on the total amount of the base resin 1
0.2 to 50 parts by weight, especially 0.5 to 50 parts by weight
When it is less than 0.2 parts by weight, the amount of acid generated at the time of exposure is small, sensitivity and resolution may be inferior, and when it exceeds 50 parts by weight, the transmittance of the resist decreases, The resolution may be poor.

As the dissolution inhibitor of the component (E), compounds having a molecular weight of 3,000 or less, whose solubility in an alkali developing solution is changed by the action of an acid, particularly low-molecular-weight phenol or carboxylic acid derivatives of 2,500 or less, are preferred. Examples thereof include compounds in which a part or the whole is substituted with an acid-labile substituent. Examples of phenol or carboxylic acid derivatives having a molecular weight of 2,500 or less include bisphenol A, bisphenol H, bisphenol S, 4,4-bis (4 ′
-Hydroxyphenyl) valeric acid, tris (4-hydroxyphenyl) methane, 1,1,1-tris (4′-hydroxyphenyl) ethane, 1,1,2-tris (4′-
Hydroxyphenyl) ethane, phenolphthalein,
Thymolphthalein and the like can be mentioned, and examples of the acid-labile substituent include those similar to the base polymer.

Examples of preferably used dissolution inhibitors include bis (4- (2'tetrahydropyranyloxy) phenyl) methane, bis (4- (2'tetrahydrofuranyloxy) phenyl) methane, bis (4- tert-butoxyphenyl) methane, bis (4-tert-butoxycarbonyloxyphenyl) methane, bis (4-te
rt-butoxycarbonylmethyloxyphenyl) methane, bis (4- (1′-ethoxyethoxy) phenyl)
Methane, bis (4- (1'-ethoxypropyloxy)
Phenyl) methane, 2,2-bis (4 ′-(2 ″ tetrahydropyranyloxy)) propane, 2,2-bis (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) propane, 2,2- Bis (4'-tert-butoxyphenyl) propane, 2,2-bis (4'-tert
-Butoxycarbonyloxyphenyl) propane, 2,
2-bis (4-tert-butoxycarbonylmethyloxyphenyl) propane, 2,2-bis (4′-
(1 ″ -ethoxyethoxy) phenyl) propane,
2,2-bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) propane, 4,4-bis (4′-
Tert-butyl (2 ″ tetrahydropyranyloxy) phenyl) valerate, tert-butyl 4,4-bis (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) valerate
-Butyl, tert-butyl 4,4-bis (4′-tert-butoxyphenyl) valerate, 4,4-bis (4-
tert-butoxycarbonyloxyphenyl) tert-butyl valerate, 4,4-bis (4′-tert-butoxycarbonylmethyloxyphenyl) valerate
tert-butyl, tert-butyl 4,4-bis (4 ′-(1 ″ -ethoxyethoxy) phenyl) valerate, 4,4
Tert-butyl bis (4 ′-(1 ″ -ethoxypropyloxy) phenyl) valerate, tris (4- (2 ′
Tetrahydropyranyloxy) phenyl) methane, tris (4- (2′tetrahydrofuranyloxy) phenyl) methane, tris (4-tert-butoxyphenyl) methane, tris (4-tert-butoxycarbonyloxyphenyl) methane, tris ( 4-tert-butoxycarbonyloxymethylphenyl) methane, tris (4- (1′-ethoxyethoxy) phenyl) methane, tris (4- (1′-ethoxypropyloxy) phenyl) methane, 1,1,2-tris (4 '-(2''
Tetrahydropyranyloxy) phenyl) ethane, 1,
1,2-tris (4 ′-(2 ″ tetrahydrofuranyloxy) phenyl) ethane, 1,1,2-tris (4 ′
-Tert-butoxyphenyl) ethane, 1,1,2-
Tris (4′-tert-butoxycarbonyloxyphenyl) ethane, 1,1,2-tris (4′-tert
-Butoxycarbonylmethyloxyphenyl) ethane,
1,1,2-tris (4 ′-(1′-ethoxyethoxy) phenyl) ethane, 1,1,2-tris (4′-
(1′-ethoxypropyloxy) phenyl) ethane and the like.

The addition amount of the dissolution inhibitor in the resist material of the present invention is optional, but is preferably 20 parts by weight or less, more preferably 15 parts by weight or less based on 100 parts by weight of the base resin in the resist material. . If the amount is more than 20 parts by weight, the heat resistance of the resist material may decrease because the monomer component increases.

Examples of the crosslinking agent as the component (F) include compounds having two or more hydroxymethyl groups, alkoxymethyl groups, epoxy groups or vinyl ether groups in the molecule, such as substituted glycouril derivatives, urea derivatives, and hexa (methoxymethyl). ) Melamine and the like are preferably used. For example, tetraalkoxymethyl-substituted glycolurils such as N, N, N ′, N′-tetramethoxymethylurea and hexamethylmelamine, tetrahydroxymethyl-substituted glycolurils and tetramethoxymethylglycoluril, Examples thereof include phenolic compounds such as hydroxymethylphenols and bisphenol A and condensates such as epichlorohydrin. Particularly suitable crosslinking agents are 1,3,5,7-tetraalkoxymethylglycoluril or 1,3,5,7-tetrahydroxymethylglycoluril, such as 1,3,5,7-tetramethoxymethylglycoluril, 2,6-dihydroxymethyl p-cresol, 2,6-dihydroxymethylphenol, 2,2 ′, 6,6′-tetrahydroxymethylbisphenol A, and 1,4-bis- [2-
(2-hydroxypropyl)]-benzene, N, N,
N ', N'-tetramethoxymethyl urea, hexamethoxymethyl melamine and the like can be mentioned. The addition amount is optional, but is preferably 1 to 1 with respect to the base resin in the resist material.
It is 25 parts by weight, more preferably 5 to 20 parts by weight. These may be used alone or in combination of two or more.

In addition to the base of the present invention, one or more bases other than the conventionally used base of the present invention can be used in combination. Conventionally used bases include primary, secondary and tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines,
Examples include a nitrogen-containing compound having a carboxy group, a nitrogen-containing compound having a sulfonyl group, a nitrogen-containing compound having a hydroxy group, a nitrogen-containing compound having a hydroxyphenyl group, an alcoholic nitrogen-containing compound, an amide derivative, and an imide derivative.

As primary aliphatic amines, ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert-amylamine, Examples thereof include cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine and the like.

The secondary aliphatic amines include dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, dicyclopentylamine, Dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-
Dimethyltetraethylenepentamine is exemplified.

The tertiary aliphatic amines include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tripentylamine and tricyclopentyl. Amine,
Trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N, N ', N'-tetramethylmethylenediamine, N, N , N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethyltetraethylenepentamine and the like.

Examples of the mixed amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine and benzyldimethylamine.

Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (for example, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline) , 3-methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline,
-Nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5-dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) Amine,
Methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene,
Pyrrole derivatives (e.g., pyrrole, 2H-pyrrole, 1
-Methylpyrrole, 2,4-dimethylpyrrole, 2,5
-Dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg, oxazole, isoxazole, etc.), thiazole derivatives (eg, thiazole, isothiazole, etc.), imidazole derivatives (eg, imidazole, 4-methylimidazole, 4-methyl-2-) Phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg, pyrroline, 2-methyl-1)
-Pyrrolidine), pyrrolidine derivatives (e.g., pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone, etc.), imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (e.g., pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine,
Phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, 4-pyrrolidinopyridine, 1- Methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives,
Piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H-indazole derivatives, indoline derivatives, quinoline derivatives (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoline derivatives, quinoxaline derivatives, phthalazine derivatives, Purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10
-Phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives, uridine derivatives and the like.

Further, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, and amino acid derivatives (for example, nicotinic acid, alanine,
Arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine, phenylalanine, threonine,
Lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like.

Examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid and pyridinium p-toluenesulfonate.

Examples of the nitrogen-containing compound having a hydroxy group, the nitrogen-containing compound having a hydroxyphenyl group, and the alcoholic nitrogen-containing compound include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, 3-indolemethanol hydrate, Monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2′-iminodiethanol, 2-aminoethanol, 3-amino-1-
Propanol, 4-amino-1-butanol, 4- (2
-Hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) ethyl] piperazine, piperidineethanol, 1- (2-hydroxy Ethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-
Propanediol, 3-pyrrolidino-1,2-propanediol, 8-hydroxyurolidine, 3-quinuclidinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2
-Hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide and the like.

The amide derivatives include formamide, N
-Methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-
Examples thereof include dimethylacetamide, propionamide, and benzamide. Examples of the imide derivative include phthalimide, succinimide, and maleimide.

Further, one or more selected from basic compounds represented by the following general formula (B) -1 can be added.

Embedded image In the formula, n = 1, 2, and 3. The side chains X may be the same or different and can be represented by the following general formulas (X) -1 to (X) -3.

[0078]

Embedded image

The side chain Y is the same or different and represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group. Further, Xs may be bonded to each other to form a ring.

Here, R ³⁰⁰ , R ³⁰² and R ³⁰⁵ have 1 to 1 carbon atoms.
4 linear, branched alkylene group, R ^301, R
^{Reference numeral 304} denotes a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, which may include one or more hydroxy groups, ether groups, ester groups, and lactone rings. R ³⁰³ is a single bond, a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms,
It may contain one or more ether, ester groups and lactone rings.

The compound represented by formula (B) -1 is specifically exemplified below. Tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, tris {2- (2-methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl {Amine, Tris} 2- (1-
Ethoxyethoxy) ethyl} amine, tris {2- (1
-Ethoxypropoxy) ethyl} amine, tris [2-
{2- (2-hydroxyethoxy) ethoxy} ethyl]
Amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.88] hexacosan, 4,7,13,18-tetraoxa-1,10-
Diazabicyclo [8.5.5] eicosan, 1,4,1
0,13-tetraoxa-7,16-diazabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-
6, tris (2-formyloxyethyl) amine, tris (2-formyloxyethyl) amine, tris (2
-Acetoxyethyl) amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, Tris (2-pivaloyloxyxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-te
rt-butoxycarbonyloxyethyl) amine, tris [2- (2-oxopropoxy) ethyl] amine, tris [2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] Amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl]
Amine, tris (2-methoxycarbonylethyl) amine, tris (2-ethoxycarbonylethyl) amine,
N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(Ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2
-Methoxyethoxycarbonyl) ethylamine, N, N
-Bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-
(Hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2
-[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-
[(Methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2-
(2-oxopropoxycarbonyl) ethylamine,
N, N-bis (2-acetoxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis ( 2
-Acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N,
N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2
-(4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(4-formyloxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2-
(2-formyloxyethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N -(2-acetoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2 -(Ethoxycarbonyl) ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl)
Ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2-
(Methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl]
Amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine,
N-methylbis (2-pivaloyloxyxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert
-Butoxycarbonyloxy) ethyl] amine, tris (methoxycarbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) Examples thereof include, but are not limited to, -δ-valerolactone.

The compounding amount of the basic compound of the present invention is preferably 0.001 to 100 parts by weight of the total base resin.
It is 2 parts by weight, particularly preferably 0.01 to 1 part by weight.
If the amount is less than 0.001 part by weight, there may be no compounding effect. If the amount exceeds 2 parts by weight, the sensitivity may be too low.

The pattern forming method of the present invention comprises a step of applying the resist material of the present invention on a substrate, and a heat treatment at preferably 50 to 200 ° C. for evaporating a solvent to solidify the film. And a step of exposing with a high-energy ray or an electron beam having a wavelength of 300 nm or less, preferably 3 to 300 nm, through the step of heating, and, if necessary, performing a heat treatment and then developing with a developer.
The heating, if necessary, is for promoting, for example, an acid-catalyzed reaction, and can be preferably performed at 50 to 180 ° C.

[0084]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. [Synthesis Example] The basic compound of the present invention was synthesized by the following method. [Synthesis Example 1] Synthesis of (N-benzyl) diethanolamine.

Embedded image 105 g of diethanolamine, 138 g of potassium carbonate,
After adding 171 g of benzyl bromide to a mixture of 1000 g of tetrahydrofuran at 20 ° C., the mixture was stirred for 20 hours. After diluting the reaction mixture with toluene, solids were separated by filtration, and the obtained filtrate was concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain 172 g of (N-benzyl) diethanolamine (88% yield).

[Synthesis Example 2] Synthesis of N-benzylbis (2-acetoxyethyl) amine

Embedded image (N-benzyl) diethanolamine 19.5 g, triethylamine 30.3 g, tetrahydrofuran 100 g
25.0 g of acetic anhydride was added to the mixture at 20 ° C., and the mixture was stirred for 5 hours. After adding 100 g of water to terminate the reaction, extraction with ethyl acetate, washing with water, and concentration under reduced pressure were performed. Purification was performed by distillation under reduced pressure to obtain 26.8 g of N-benzylbis (2-acetoxyethyl) amine (yield: 96%).

Synthesis Example 3 Synthesis of N, N-bis (2-methoxyethyl) p-methoxybenzylamine

Embedded image N, N-bis (2-methoxyethyl) p- was obtained in the same manner as in Synthesis Example 1 except that bis (2-methoxyethyl) amine was used instead of diethanolamine and p-methoxybenzylamine was used instead of benzyl bromide. Methoxybenzylamine was obtained (yield 90%).

Synthesis Example 4 Synthesis of N- (3,5-dimethoxybenzyl) bis (2-acetoxyethyl) amine

Embedded image N- (3,5-dimethoxybenzyl) bis (2-acetoxyethyl) amine was obtained in the same manner as in Synthesis Examples 1 and 2, except that 3,5-dimethoxybenzyl bromide was used instead of benzyl bromide ( Yield 82%).

[Synthesis Example 5] Synthesis of methyl 3,3 '-(benzylimino) dipropionate.

Embedded image To a mixture of 94.7 g of methyl acrylate and 50 g of methanol was added 53.6 g of benzylamine.
Left for hours. After concentration under reduced pressure, purification was performed by distillation under reduced pressure to obtain 135 g of methyl 3,3 ′-(benzylimino) dipropionate (boiling point: 131 ° C./31 Pa, yield: 97)
%). IR (thin film): ν = 3086, 3028, 2992,
953, 2837, 1738, 1603, 1495, 1
437,1356,1331,1250,1196,1
^{174,1130,1043,739,698cm -1 1 H-NMR (300MHz} in CDCl 3): δ
= 2.47 (4H, t, J = 7.2 Hz), 2.80
(4H, t, J = 7.2 Hz), 3.58 (2H,
s), 3.64 (6H, s), 7.20-7.35 (5
H, m).

Synthesis Example 6 Synthesis of 3,3 ′-(benzylimino) dipropionitrile

Embedded image 3,3 ′-(benzylimino) dipropionitrile was synthesized in the same manner as in Synthesis Example 5 except that acrylonitrile was used instead of methyl acrylate (boiling point: 16)
2 ° C./24 Pa, yield 93%). IR (thin film): ν = 3085, 3062, 3030, 2
953, 2933, 2837, 2247, 1603, 1
496, 1454, 1421, 1373, 1335, 1
263, 1134, 1078, 1028, 737, 70
^{0cm -1 1 H-NMR (300MHz} in CDCl 3): δ
= 2.46 (4H, t, J = 6.9 Hz), 2.90
(4H, t, J = 6.9 Hz), 3.72 (2H,
s), 7.20-7.40 (5H, m).

[Synthesis Example 7] Synthesis of methyl 3,3 '-(2-p-hydroxyphenylethylimino) dipropionate.

Embedded image Methyl 3,3 ′-(2-p-hydroxyphenylethylimino) dipropionate was prepared in the same manner as in Synthesis Example 5 except that 2-p-hydroxyphenylethylamine was used instead of benzylamine and distillation under reduced pressure was not performed. Was synthesized (quantitative yield).

[Synthesis Example 8] Synthesis of ethyl 3,3 '-(3,4,5-trimethoxybenzylimino) dipropionate.

Embedded image 3,3 ′-(3,4,5,5) was obtained in the same manner as in Synthesis Example 5 except that ethyl acrylate was used instead of methyl acrylate and 3,4,5-trimethoxybenzylamine was used instead of benzylamine. (Trimethoxybenzylimino) dipropionate ethyl was synthesized (yield 84%).

[Synthesis Example 9] Synthesis of N-benzylmorpholine.

Embedded image To a mixture of 192 g of morpholine and 1000 g of tetrahydrofuran was added 171 g of benzyl bromide at 20 ° C., followed by stirring for 16 hours. After dilution with ether, the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain 168 g of N-benzylmorpholine (boiling point: 64 ° C./40 Pa, yield: 95).
%). IR (thin film): ν = 3062, 3028, 2956, 2
893, 2852, 2806, 2764, 1603, 1
496, 1454, 1396, 1351, 1315, 1
286,1263,1117,1070,1009,9
^{14,866,804,741,698cm -1 1 H-NMR (300MHz} in CDCl 3): δ
= 2.45 (4H, m), 3.51 (2H, s), 3.
72 (4H, m), 7.20-7.35 (5H, m).

[Synthesis Example 10] Synthesis of N-phenylmorpholine.

Embedded image N-phenylmorpholine was synthesized in the same manner as in Synthesis Example 8, except that benzene bromide was added instead of benzyl bromide.

[Examples and Comparative Examples] Evaluation example of resist A polymer, an acid generator, a base, a dissolution inhibitor and a cross-linking agent were used as propylene glycol monomethyl ether acetate (PG
MEA) and ethyl lactate (EL) were dissolved in a 70:30 weight ratio mixed solvent at the composition shown in Tables 1-3, and 0.1 μm was dissolved.
A resist solution was prepared by filtration through a size Teflon filter. Next, the obtained resist solution is formed into a film of DUV-30 (manufactured by Nissan Chemical Industries, Ltd.) on a silicon wafer to a thickness of 55 nm, and the film is subjected to KrF light (248).
nm), and the substrate was baked at 100 ° C. for 90 seconds using a hot plate to reduce the thickness of the resist to 550 nm. This is excimer laser stepper (Nikon, N
Exposure was performed using SR-S202A, NA-0.60, σ0.75 (normal illumination) while changing the exposure amount and focus, and immediately after exposure, baked at 110 ° C. for 90 seconds.
The pattern was obtained by developing with a 38% aqueous solution of tetramethylammonium hydroxide for 60 seconds.

The obtained resist pattern was evaluated as follows. The results are shown in Tables 1 to 3. Evaluation method: 0.18 μm line and space:
The exposure amount resolved at 1 is defined as an optimum exposure amount (Eop) (this is referred to as sensitivity), and a focus margin Do at this time is set.
F (μm) was determined. The definition of the focus margin is that the film of the pattern does not decrease and the dimension is 0.18 μm ±.
It was determined that the size was within 10%. Next, after the development.
The length of the isolated line was measured at an exposure amount at which the line and space 1: 1 of 18 μm was completed according to the size, and the I / G bias was obtained by subtracting the size of the isolated pattern from the size of the line and space pattern.

[0096]

It has been found that the resist containing a base of the present invention has excellent characteristics such as a wide focus margin and a small I / G bias (a dimensional difference between a dense pattern and an isolated pattern).

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

Embedded image

[0101]

Embedded image

[0102]

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[0103]

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[0104]

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[0105]

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[Brief description of the drawings]

FIG. 1 shows line dimensions when the pitch of a 0.18 micron line is changed.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 295/02 C07D 295/02 G03F 7/004 501 G03F 7/004 501 7/038 601 7/038 601 7 / 039 601 7/039 601 H01L 21/027 H01L 21/30 502R (72) Inventor Takeshi Nagata 28-28, Nishifukushima, Oku, Kushiro-mura, Nakakibijo-gun, Niigata Synthetic Technology Research Laboratory, Shin-Etsu Chemical Co., Ltd. (72) Inventor Kazuki Maeda 1 at 28 Nishifukushima, Nishifukushima, Oaza, Nakatsukushi-gun, Niigata Prefecture Inside the Synthetic Research Laboratory, Shin-Etsu Chemical Co., Ltd. 1 Shin-Etsu Chemical Co., Ltd. Synthetic Technology Laboratory F-term (reference) 2H025 AA00 AA02 AB16 AC04 AC05 AC06 AC08 AD01 AD03 BE00 BG00 CC03 CC20 FA03 FA12 FA17 4H006 AA01 AA03 AB92 BJ50 BN10 BP10 BT12 BU38 BU40 QN30

Claims (8)

[Claims] 1. A basic compound represented by the following general formula (1). Embedded image (In the above formula, R ⁰ is a linear or branched alkyl group having 1 to 6 carbon atoms, and may include a hydroxy group, an ether group, a carbonyl group, an ester group, a lactone ring, or a carbonate group. Is 1 or 2, b is 1 or 2, and a + b = 3 is satisfied.) 2. A basic compound represented by the following general formula (2). Embedded image (In the above formula, a is 1 or 2, b is 1 or 2,
And a + b = 3 is satisfied. ) 3. A basic compound represented by the following general formula (3). Embedded image (In the above formula, X is an oxygen atom or a sulfur atom.) 4. A resist material containing one or more basic compounds selected from the group consisting of the following general formulas (5) to (9). Embedded image (Wherein R ¹ is independently an aryl or aralkyl group having 6 to 20 carbon atoms, such as a hydroxy group, an ether group,
It may contain a carbonyl group, an ester group, a lactone ring, or a carbonate group. R ² , R ⁴ and R ⁷ are each independently a linear or branched alkylene group having 1 to 4 carbon atoms. R ³ and R ⁶ are each independently a hydrogen atom or a group having 1 to 2 carbon atoms.
0 linear, an alkyl group or an alkoxy group of branched or cyclic, hydroxy group, an ether group, a carbonyl group, an ester group, may contain a lactone ring, or a carbonate group, R ⁵ is independently A single bond or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁸ is independently a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, including a hydroxy group, an ether group, a carbonyl group, an ester group, a lactone ring, a carbonate group, or a cyano group. You can go out. R ⁷
And R ⁸ may combine with each other to form a ring. R ⁹ is independently a linear or branched alkylene group having 1 to 20 carbon atoms, and includes at least one or more hydroxy group, ether group, carbonyl group, ester group, thioether group, and carbonate. a is independently 1 or 2, and b is independently 1 or 2, but in each compound a
+ B = 3. 5. An alkali-insoluble or poorly-soluble resin having an organic solvent and an acidic functional group protected by an acid labile group, wherein the resin becomes alkali-soluble when the acid labile group is eliminated. The positive resist material according to claim 4, comprising a base resin and an acid generator. 6. The method according to claim 5, further comprising a dissolution inhibitor.
A positive resist material according to item 1. 7. A negative-working composition comprising an organic solvent, an alkali-soluble resin, a base resin which becomes hardly soluble in alkali by crosslinking with a crosslinking agent, an acid generator, and a crosslinking agent which is crosslinked by acid. The resist material according to claim 4, which is: 8. A step of applying the resist material according to any one of claims 5 to 7 on a substrate;
A pattern forming method comprising: a step of exposing with a high-energy ray having a wavelength of 300 nm or less or an electron beam via a photomask;